Design, Synthesis, and Bioactivation of O-Glycosylated Prodrugs of the Natural Nitric Oxide Precursor N(ω)-Hydroxy-l-arginine

J Med Chem. 2016 Sep 8;59(17):8030-41. doi: 10.1021/acs.jmedchem.6b00810. Epub 2016 Aug 29.

Abstract

Naturally occurring N(ω)-hydroxy-l-arginine (NOHA, 1) is the best substrate of NO synthases (NOS). The development of stable and bioavailable prodrugs would provide a pharmacologically valuable strategy for the treatment of cardiovascular diseases that are associated with endothelial dysfunction. To improve NOHAs druglike properties, we demonstrate that O-substitution by (glycosylic) acetal formation greatly increased the chemical stability of the hydroxyguanidine moiety and provided a nontoxic group that could be easily bioactivated by glycosidases. A straightforward synthetic concept was devised and afforded a series of diversely substituted prodrugs by O-conjugation of the hydroxyguanidine moiety with different monosaccharides. Systematic exploration of their bioactivation profile revealed that glucose-based prodrugs were more efficiently bioactivated than their galactose counterparts. NOS-dependent cytosolic NO release was quantified by automated fluorescence microscopy in a cell-based assay with murine macrophages. Glucose-based prodrugs performed particularly well and delivered cellular NO levels comparable to 1, demonstrating proof-of-concept.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Arginine / analogs & derivatives*
  • Arginine / chemical synthesis
  • Arginine / chemistry
  • Arginine / pharmacology
  • Cell Line
  • Drug Design
  • Galactose / chemistry
  • Glucose / chemistry
  • Glycosylation
  • Macrophages / drug effects
  • Macrophages / metabolism
  • Mice
  • Nitric Oxide / metabolism
  • Nitric Oxide Donors / chemical synthesis
  • Nitric Oxide Donors / chemistry*
  • Nitric Oxide Donors / pharmacology
  • Nitric Oxide Synthase / metabolism
  • Prodrugs / chemical synthesis
  • Prodrugs / chemistry*
  • Prodrugs / pharmacology
  • Stereoisomerism
  • Structure-Activity Relationship

Substances

  • Nitric Oxide Donors
  • Prodrugs
  • Nitric Oxide
  • N(omega)-hydroxyarginine
  • Arginine
  • Nitric Oxide Synthase
  • Glucose
  • Galactose